This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2000-202488, filed Jul. 4, 2000, the entire contents of which are incorporated herein by reference.
The present invention relates to a novel color coupler compound and further to a silver halide color photographic lightsensitive material containing the same and a method of forming an image with the use thereof. More particularly, the present invention relates to a silver halide color reversal photographic lightsensitive material and a method of forming an image with the use thereof.
In recent years, there is a strong demand for a silver halide color lightsensitive material exhibiting not only high sensitivity, high sharpness and excellent graininess but also enhanced color reproduction.
In the field of silver halide color photographic lightsensitive materials, although 1-phenyl-5-pyrazolone couplers have widely been employed as magenta couplers, pyrazolotriazole magenta couplers which form a dye of hue with less secondary absorption, preferred as an image forming dye, have also become widely employed.
Although pyrazolotriazole magenta couplers are attractive compounds in their characteristics of exhibiting desirable hue, those wherein the position for coupling with an aromatic primary amine developing agent in an oxidized form is a hydrogen atom, generally known as four-equivalent couplers, have a drawback in that yellow coloring would occur with the passage of time after the development thereof.
On the other hand, two-equivalent couplers wherein the coupling position is substituted with a coupling split-off group other than a hydrogen atom (e.g., a halogen atom) have the characteristic of exhibiting less tendency toward yellow coloring as compared with that of the four-equivalent couplers.
With respect to a color reversal photographic lightsensitive material, the first development is followed by the reversal processing and the color development in this sequence. The use of two-equivalent couplers in the color reversal photographic lightsensitive material invites an intrinsic problem of sensitivity decrease as compared with the use of four-equivalent couplers because the color forming capability per mol of silver is high in the use of two-equivalent couplers. Therefore, when the pyrazolotriazole magenta couplers are applied to the color reversal photographic lightsensitive material, it is preferred to employ the four-equivalent couplers from the viewpoint of sensitivity. The application of four-equivalent pyrazolotriazole magenta couplers to a color reversal photographic lightsensitive material is disclosed in, for example, Jpn. Pat. Appln. KOKAI Publication Nos. (hereinafter referred to as JP-A""s) 5-100382 and 63-153548. However, the above-mentioned problem of yellow coloring with the passage of time after the processing has not yet been solved. In particular, it has been a problem that an increase of yellow stain is caused when a sample having been allowed to stand still for a prolonged period of time after the processing is irradiated with light. With respect to this stain, an improvement can be effected by changing a partial structure of coupler, but it has been unsatisfactory.
It is an object of the present invention to provide a silver halide color photographic lightsensitive material which is excellent in color reproduction and in image fastness (fastness to light and fastness to dark heat) and which minimizes staining.
It is another object of the present invention to provide a color reversal photographic lightsensitive material which is excellent in the storagebility of lightsensitive material and is highly resistant to development processing composition variations. It is a further object of the present invention to effect an improvement in the yellow stain occurring when a sample having been allowed to stand still for a prolonged period of time after the processing is irradiated with light.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
The inventors have conducted extensive and intensive studies with respect to additives used in combination with four-equivalent pyrazolotriazole couplers. As a result, it has been found that a compound of specified structure suppresses staining and, in particular, effectively suppresses the stain occurring when a sample having been allowed to stand still for a prolonged period of time after the processing is irradiated with light. It has further been found that the fastness of color image can also been enhanced thereby. The present invention has been completed on the basis of these findings.
The above objects of the present invention have been attained by the following means.
(1) A silver halide color photographic lightsensitive material comprising, on a support, at least one silver halide emulsion layer, wherein the silver halide color photographic lightsensitive material contains
at least magenta coupler represented by a general formula (MC-I): 
wherein, each of R31 and R32 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; and
at least one compound selected from a group consisting of compounds represented by a general formula (TS-I), compounds represented by a general formula (TS-II) and compounds represented by a general formula (TS-III): 
wherein in the formula (TS-I), R1 represents any of a hydrogen atom, a substituted or unsubstituted alkyl group (including a cycloalkyl group and a bicycloalkyl group), a substituted or unsubstituted alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylsulfonyl group (including a cycloalkylsulfonyl group and a bicycloalkylsulfonyl group), a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinyl group and a group of the formula xe2x80x94SiR21R22R23 wherein each of R21, R22 and R23 independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group or a substituted or unsubstituted aryloxy group; xe2x80x94X1xe2x80x94 represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94N(R24)xe2x80x94 wherein R24 has the same meaning as R1; and R2, R3, R4, R5 and R6 may be identical with or different from each other, and each thereof represents a hydrogen atom or a substituent, provided that R1 and R2, or R24 and R6, or R1 and R24, may be bonded with each other to thereby form a 5 to 7 membered ring, provided that R2 and R3, or R3 and R4, or R4 and R5, or R5 and R6, may be bonded with each other to thereby form a 5 to 7 membered ring, Spiro ring or bicyclo ring, and provided that R1, R2, R3, R4, R5, R6 and R24 are not simultaneously hydrogen atoms;
in the formula (TS-II), each of R11, R12, R13 and R14 independently represents any of a hydrogen atom, a substituted or unsubstituted alkyl group (including a cycloalkyl group and a bicycloalkyl group) and a substituted or unsubstituted alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), provided that R11 and R12 or R13 and R14 may be bonded with each other to thereby form a 5 to 7 membered ring; X2 represents any of a hydrogen atom, a substituted or unsubstituted alkyl group (including a cycloalkyl group and a bicycloalkyl group), a substituted or unsubstituted alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), a substituted or unsubstituted alkoxy group (including a cycloalkyloxy group), substituted or unsubstituted alkenyloxy group, alkyl- and alkenyloxycarbonyl groups, a substituted or unsubstituted aryloxycarbonyl group, acyl groups, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkyloxycarbonyloxy group, a substituted or unsubstituted alkenyloxycarbonyloxy group, substituted or unsubstituted aryloxycarbonyloxy group, alkyl- and alkenylsulfonyl groups, substituted or unsubstituted arylsulfonyl group, alkyl- and alkenylsulfinyl groups, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a hydroxyl group and an oxyl group; and X3 represents a group of nonmetallic atoms required for forming a 5 to 7 membered ring; and
in the formula (TS-III), each of R21 and R22 independently has the same meaning as R1; X4 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, xe2x80x94COxe2x80x94R123, xe2x80x94COxe2x80x94Oxe2x80x94R123 or xe2x80x94COxe2x80x94NR124 (R125) wherein R123 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and each of R124 and R125 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted alkoxy group.
(2) A method of forming a color image, comprising sequentially subjecting the silver halide color photographic lightsensitive material as defined in item (1) above to black and white development, reversal processing and color development using a color developer of 11.5 or higher pH value, wherein the color developer is replenished in a quantity of less than 1.6 L per m2 of the lightsensitive material.
(3) A method of reducing stain caused by light irradiation after the elapse of a prolonged period of time after processing in a silver halide color photographic lightsensitive material containing a magenta coupler represented by a general formula (MC-I): 
wherein R31 and R32 have the same meanings as those defined in the formula (MC-I) of the item (1) above, respectively; wherein the method comprises loading the silver halide color photographic lightsensitive material with at least one compound selected from a group consisting of compounds represented by the general formula (TS-I), the general formula (TS-II) and general formula (TS-III): 
xe2x80x83wherein
R1, R2, R3, R4, R5, R6 and xe2x80x94X1xe2x80x94 have the same meanings as those defined in the general formula (TS-I) of the item (1) above, respectively;
R11, R12, R13, R14, X2 and X3 have the same meanings as those defined in the general formula (TS-II) of the item (1) above, respectively; and
R21, R22 and X4 have the same meanings as those defined in the general formula (TS-III) of the item (1) above, respectively.
(4) A silver halide color photographic lightsensitive material comprising a layer simultaneously loaded with a magenta coupler represented by the following general formula (MC-I) and a compound represented by the following general formula (TS-III): 
xe2x80x83wherein,
R31 and R32 have the same meanings as those of the general formula (MC-I) of the item (1) above, respectively, and
in R21, R22 and X4 have the same meanings as those of the general formula (TS-III) of the item (1) above, respectively.
The present invention will be described in detail below.
In the general formula (MC-I), each of R31 and R32 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
When each of R31 and R32 is a substituted alkyl or aryl group, the substituent that attaches to each of R31 and R32 can be, for example, any of a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, alkyl- and arylsulfonylamino groups, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, alkyl- and arylsulfinyl groups, alkyl- and arylsulfonyl groups, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, aryl and heterocyclic azo groups, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group and a silyl group.
More specifically, the substituent of the substituted R31 and R32 can be a halogen atom (e.g., a chlorine atom, bromine atom, and iodine atom), and an alkyl group [which represents a straight-chain, branched, or cyclic, substituted or unsubstituted alkyl group. Examples are an alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g., cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples are bicyclo[1,2,2]heptane-2-yl and bicyclo[2,2,2]octane-3-yl). Also an alkyl group having more cyclic structure such as a tricyclic alkyl group is included. The alkyl group to be described below, such as the alkyl group of an alkylthio group, also includes the concept of the alkyl group mentioned above.]
The substituent of the substituted R31 and R32 can also be alkenyl group [which represents a straight-chain, branched, or cyclic, substituted or unsubstituted alkenyl group. Examples are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, e.g., vinyl, allyl, prenyl, geranyl, and oleyl), cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms. Examples are 2-cyclopentene-1-yl and 2-cyclohexene-1-yl), bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom from bicycloalkene having one double bond. Examples are bicyclo[2,2,1]hept-2-ene-1-yl and bicyclo[2,2,2]oct-2-ene-4-yl)].
The substituent of the substituted R31 and R32 can also be an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, and trimethylsilylethynyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl), heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered, substituted or unsubstituted, aromatic or nonaromatic heterocyclic compound, and more preferably, a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples are 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, and alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, e.g., methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, and 2-methoxyethoxy).
The substituent of the substituted R31 and R32 can also be an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, and 2-tetradecanoylaminophenoxy), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, e.g., trimethylsilyloxy and t-butyldimethylsilyloxy), heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, e.g., 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy), and acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 7 to 30 carbon atoms, e.g., formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy).
The substituent of the substituted R31 and R32 can also be a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, e.g., N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, e.g., methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy), and aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, e.g., phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-(n-hexadecyloxy)phenoxycarbonyloxy).
The substituent of the substituted R31 and R32 can also be an amino group (including an anilino group) (preferably an unsubstituted amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, e.g., methylamino, dimethylamino, anilino, N-methyl-anilino, and diphenylamino), acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 7 to 30 carbon atoms, e.g., acetylamino, pivaloylamino, lauroylamino, benzoylamino, and 3,4,5-tri-(n-octyloxyphenyl)carbonylamino), and aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, e.g., carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino).
The substituent of the substituted R31 and R32 can also be an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, e.g., methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, e.g., phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-(n-octyloxy)phenoxycarbonylamino), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, e.g., sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino).
The substituent of the substituted R31 and R32 can also be an alkylsulfonylamino and arylsulfonylamino groups (preferably a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, e.g., methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, e.g., methylthio, ethylthio, and n-hexadecylthio), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, e.g., phenylthio, p-chlorophenylthio, and m-methoxyphenylthio), and heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, to which an aromatic ring such as a benzene ring may be condenced, e.g., 2-benzothiazolylthio and 1-phenyl-tetrazole-5-ylthio).
The substituent of the substituted R31 and R32 can also be a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, e.g., N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N-(Nxe2x80x2-phenylcarbamoyl)sulfamoyl), sulfo group, alkylsulfinyl and arylsulfinyl groups (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, e.g., methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl).
The substituent of the substituted R31 and R32 can also be an alkylsulfonyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, e.g., methylsulfonyl, ethylsulfonyl, phenylsulfonyl, and p-methylphenylsulfonyl), acyl group (preferably a formyl group substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a substituted or unsubstituted heterocycliccarbonyl group, whose carbon atom in the heterocyclic ring bonds to the carbonyl group thereof, e.g., acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-(n-octyloxy)phenylcarbonyl, 2-pyridylcarbonyl and 2-furylcarbonyl), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, e.g., phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-(t-butyl)phenoxycarbonyl), and an alkoxycarbonyl group (e.g., a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl).
The substituent of the substituted R31 and R32 can also be a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, e.g., carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-(n-octyl)carbamoyl, and N-(methylsulfonyl)carbamoyl), arylazo and heterocyclic azo groups (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, and a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, e.g., phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazole-2-ylazo), imide group (preferably N-succinimide and N-phthalimide), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, e.g., dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino), and phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, e.g., phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl).
The substituent of the substituted R31 and R32 can also be a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, e.g., diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, e.g., dimethoxyphosphinylamino and dimethylaminophosphinylamino), and silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g., trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl).
Of the above substituents, those having a hydrogen atom may be further substituted by the above groups by removing the hydrogen atom. Examples of such substituents are an alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group, and arylsulfonylaminocarbonyl group. Examples of these groups are methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and a benzoylaminosulfonyl group.
In the general formula (MC-I), R31 preferably represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. More preferably, R31 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Still more preferably, R31 represents an unsubstituted tertiary or secondary alkyl group having 3 to 6 carbon atoms. Yet still more preferably, R31 represents an unsubstituted tertiary alkyl group having 4 to 6 carbon atoms. Most preferably, R31 represents a t-butyl group.
R32 preferably represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. More preferably, R32 represents a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms. Still more preferably, R31 represents a substituted alkyl group having 2 to 30 carbon atoms.
The substituent introduced in the substituted R32 can be any of acylamino groups, alkyl- and arylsulfonylamino groups, alkoxycarbonylamino groups and aminocarbonylamino groups. These may be further substituted with the substituent described as being introduced as the substituent in the substituted R32.
Preferred forms of the structures represented by the general formula (MC-I) are those represented by the following general formula (MC-II): 
In the general formula (MC-II), R31 has the same meaning as the R31 of the general formula (MC-I). L1 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group. L2 represents xe2x80x94SO2xe2x80x94 or xe2x80x94COxe2x80x94. L3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group. R33 has the same meaning as the R2 of the general formula (TS-I) (provided that a hydrogen atom is excluded). n is an integer of 0 to 5. When n is 2 or greater, a plurality of R33 groups may be identical with or different from each other.
In the general formula (MC-II), R31 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R31 preferably represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. More preferably, R31 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Still more preferably, R31 represents an unsubstituted tertiary or secondary alkyl group having 3 to 6 carbon atoms. Yet still more preferably, R31 represents an unsubstituted tertiary alkyl group having 4 to 6 carbon atoms. Most preferably, R31 represents a t-butyl group.
L1 preferably represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. The substituent introduced in the substituted L1 can be, for example, any of groups described as the substituent of the substituted R31 and R32 of the general formula (MC-I). L1 more preferably represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms. The substituent introduced in the substituted alkylene group is preferably an alkoxy group, an aryloxy group or a halogen atom.
Still more preferably, L1 represents an unsubstituted alkylene group having 1 to 10 carbon atoms. Yet still more preferably, L represents an unsubstituted alkylene group having 1 to 3 carbon atoms (methylene, 1,2-ethylene, 1,3-propylene, 1-methylmethylene, 1,1-dimethylmethylene or 2-methyl-1,2-ethylene). Most preferably, L1 represents 1-methylmethylene.
L2 represents xe2x80x94SO2xe2x80x94 or xe2x80x94COxe2x80x94, preferably xe2x80x94SO2xe2x80x94.
L3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group. L3 preferably represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. The substituent introduced in the substituted L3 can be, for example, any of groups described as the substituent in the substituted R31 and R32 of the general formula (MC-I).
More preferably, L3 represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. Still more preferably, L3 represents a substituted or unsubstituted arylene group having 6 to 16 carbon atoms. The substituent introduced in the substituted L3 is preferably an alkoxy group, an aryloxy group, a halogen atom or an alkyl group.
R33 has the same meaning as the R2 of the general formula (TS-I). R33 is preferably an electron attractive substituent whose Hammett""s constant up value is 0 or greater. In particular, R33 preferably represents a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group.
n is an integer of 0 to 5. When n is 2 or greater, a plurality of R33 groups may be identical with or different from each other. n is preferably 1 or 2. When n=1, the substitution position of R33 is preferably m-position to xe2x80x94NHxe2x80x94SO2xe2x80x94. When n=2, it is preferably o- or m-position to xe2x80x94R33. More preferably, the substitution positions are 2,5-positions or 3,5-positions, providing that xe2x80x94NHxe2x80x94SO2xe2x80x94 lies at 1-position. n is most preferably 2.
In a preferred form of the general formula (MC-II), R31 represents an unsubstituted tertiary alkyl group having 3 to 6 carbon atoms. L1 represents an unsubstituted alkylene group having 1 to 3 carbon atoms. L2 represents xe2x80x94SO2xe2x80x94 or xe2x80x94COxe2x80x94. L3 represents a substituted or unsubstituted arylene group having 6 to 16 carbon atoms. R33 represents a halogen atom, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. n is 1 or 2.
In a more preferred form of the general formula (MC-II), R31 represents a t-butyl group. L1 represents an unsubstituted alkylene group having 1 to 3 carbon atoms. L2 represents xe2x80x94SO2xe2x80x94. L3 represents an arylene group substituted with an alkoxy group having 6 to 26 carbon atoms. R33 represents a carbamoyl group or an alkoxycarbonyl group. n is 1 or 2.
With respect to the couplers of the present invention, specific compound examples will be given below, to which the present invention is in no way limited.
The couplers of the general formula (MC-1) of the present invention can be synthesized by known methods, for example, those described in U.S. Pat. Nos. 4,540,654, 4,705,863 and 5,451,501, JP-A""s 61-65245, 62-209457, 62-249155 and 63-41851, Jpn. Pat. Appln. KOKOKU Publication Nos. (hereinafter referred to as JP-B""s) 7-122744, 5-105682, 7-13309 and 7-82252, U.S. Pat. Nos. 3,725,067 and 4,777,121, JP-A""s 2-201442, 2-101077, 3-125143 and 4-242249.
In the general formula (TS-I), it is preferred that R1 represent any of a hydrogen atom, substituted or unsubstituted alkyl groups (including a cycloalkyl group and a bicycloalkyl group), substituted or unsubstituted alkenyl groups (including a cycloalkenyl group and a bicycloalkenyl group) and substituted or unsubstituted aryl groups.
xe2x80x94X1xe2x80x94 preferably represents xe2x80x94Oxe2x80x94 or xe2x80x94N(R24)xe2x80x94, wherein R24 preferably represents a substituted or unsubstituted alkyl group.
Preferably, R2, R3, R4, R5 and R6 may be identical with or different from each other, and each thereof represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acylamino group, or a halogen atom.
Among the compounds of the general formula (TS-I), those represented by the following formulae (TS-I-xcex1) and (TS-I-xcex2) are preferred: 
In the formula (TS-I-xcex1), R2, R3, R5 and R6 each independently have the same meaning as the R2, R3, R5 and R6 of the general formula (TS-I). X1a and X1b each independently have the same meaning as the X1 of the general formula (TS-I). R1a and R1b each independently have the same meaning as the R1 of the general formula (TS-I).
In the formula (TS-I-xcex2), R3a, R3b, R4a, R4b, R5a, R5b, R6a and R6b each independently have the same meaning as the R3, R4, R5 and R6 of the general formula (TS-I). X1c and X1d each independently have the same meaning as the X1 of the general formula (TS-I). R1c and R1d each independently have the same meaning as the R1 of the general formula (TS-I). L4 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.
Among the compounds of the formula (TS-I-xcex1), those wherein each of R2, R3, R5 and R6 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or an acylamino group having 1 to 20 carbon atoms are preferred. Preferably, each of X1a and X1b independently represents xe2x80x94Oxe2x80x94 or xe2x80x94N(R24)xe2x80x94, wherein R24 preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Further, preferably, each of R1a and R1b independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
More preferably, X1a and X1b simultaneously represent xe2x80x94Oxe2x80x94, or the one thereof represents xe2x80x94N(R24)xe2x80x94 while the other represents xe2x80x94Oxe2x80x94. Further, more preferably, R1a and R1b represent substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.
Among the compounds of the formula (TS-I-xcex2), those wherein each of R3a, R3b, R4a, R4b, R5a, R5b, R6a and R6b independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom or an acylamino group having 1 to 20 carbon atoms are preferred. Preferably, each of X1c and X1d independently represents xe2x80x94Oxe2x80x94. Further, preferably, each of R1c and R1d independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an acylamino group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkenyl group having 3 to 20 carbon atoms. L4 preferably represents an unsubstituted alkylene group having 1 to 20 carbon atoms.
More preferably, R1c and R1d simultaneously represent hydrogen atoms, and R3a, R3b, R4a, R4b, R5a, R5b, R6a and R6b simultaneously represent hydrogen atoms. Further, more preferably, L4 represents an unsubstituted alkylene group having 1 to 8 carbon atoms.
In a preferred form of the structure of compound of the formula (TS-I-xcex2), each of R4a, R4b, R6a and R6b independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms. R1c, R1d, R3a, R3b, R5a and R5b simultaneously represent hydrogen atoms. X1c and X1d simultaneously represent xe2x80x94Oxe2x80x94. L4 represents an unsubstituted alkylene group having 1 to 8 carbon atoms.
Among the compounds of the general formula (TS-II), those wherein each of R11, R12, R13 and R14 represents an unsubstituted alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms are preferred. More preferably, R11, R12, R13 and R14 are the same and represent an unsubstituted alkyl group having 1 to 3 carbon atoms. Still more preferably, R11, R12, R13 and R14 simultaneously represent a methyl group. R11 and R12, or R13 and R14, may be bonded with each other to thereby form a 5 to 7 membered ring. X2 preferably represents any of a hydrogen atom, alkyl groups (including a cycloalkyl group and a bicycloalkyl group), alkenyl groups (including a cycloalkenyl group and a bicycloalkenyl group), alkoxy groups (including a cycloalkyloxy group), acyl groups, acyloxy groups, a hydroxyl group and an oxyl group. X2 more preferably represents an unsubstituted alkoxy group having 1 to 20 carbon atoms (including a cycloalkyloxy group) or an oxyl group. X3 preferably represents an atom group required for forming a nitrogen containing 6-membered ring.
In a preferred form of the general formula (TS-II), R11, R12, R13 and R14 simultaneously represent a methyl group. X2 represents an unsubstituted alkoxy group having 1 to 20 carbon atoms (including a cycloalkyloxy group) or an oxyl group. X3 represents an atom group required for forming a nitrogen containing 6-membered ring.
In the general formula (TS-III), each of R21 and R22 independently has the same meaning as the above R1. R21 preferably represents a hydrogen atom. R22 preferably represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R22 more preferably represents an unsubstituted alkyl group having 1 to 5 carbon atoms. X4 preferably represents xe2x80x94COxe2x80x94R123, xe2x80x94COxe2x80x94Oxe2x80x94R123 or xe2x80x94COxe2x80x94NR124(R125) wherein R123 preferably represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Preferably, each of R124 and R125 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. X4 most preferably represents xe2x80x94COxe2x80x94R123, wherein R123 represents a substituted or unsubstituted alkyl group.
Among the compounds of the general formula (TS-III), those wherein R21 represents a hydrogen atom, R22 represents an unsubstituted alkyl group having 1 to 5 carbon atoms and X4 represents xe2x80x94COxe2x80x94R123, xe2x80x94COxe2x80x94Oxe2x80x94R123 or xe2x80x94COxe2x80x94NR124(R125), in which R123 represents a substituted or unsubstituted alkyl group while each of R124 and R125 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, are preferred.
Among the compounds represented by the general formula (TS-I), the compounds represented by the general (TS-II) and the compounds represented by the general (TS-III), preventives having the structure of the general formula (TS-III) are highly effective and preferred.
One or two or more compounds represented by the general formula (TS-I) can be incorporated in the lightsensitive material. The compounds can be incorporated in the same layer or in different layers. This is also true with respect to the compounds represented by the general formula (TS-II) or (TS-III). Further, the lightsensitive material can be simultaneously loaded with the compounds of the general formulae (TS-I), (TS-II) and (TS-III). It is preferred to incorporate at least one compound selected from the compound of the general formulae (TS-I), (TS-II) and (TS-III), and the coupler of the general formula (MC-I) in the same layer.
The molecular weight of each of the compounds of the general formulae (TS-I), (TS-II) and (TS-III) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, and most preferably 300 or more. The molecular weight is preferably 1000 or less, more preferably 800 or less. The addition amount of each of the compounds of the general formulae (TS-I), (TS-II) and (TS-III) is in the range of 0.05 to 50 mol/m2, preferably 0.1 to 10 mol/m2, and more preferably 0.5 to 5 mol/m2. It is preferred that the compounds of the general formulae (TS-I), (TS-II) and (TS-III) be added to the layer wherein the coupler of the general formula (MC-I) is contained. The compounds are added in an amount of 1 to 300 mmol %, preferably 10 to 100 mmol %, based on the total amount of the coupler contained in the layer.
With respect to the preventives of the general formulae (TS-I), (TS-II) and (TS-III), compound examples will be given below. The present invention is in no way limited to the compound examples given below. 
Compounds of the general formulae (TS-I), (TS-II) and (TS-III) are known, and relevant patents are cited in, for example, Research Disclosure Nos. 17643 (IV, items I to J), 15162, 18716 (page 650, left column), 36544 (page 527), 307105 (page 872) and 15162.
The coupler of the general formula (MC-I) or (MC-II) according to the present invention is incorporated in the lightsensitive material in an amount of 0.01 to 10 g, preferably 0.1 to 2 g, per m2 of lightsensitive material. The coupler is appropriately incorporated in the lightsensitive material in an amount of 1xc3x9710xe2x88x923 to 1 mol, preferably 2xc3x9710xe2x88x923 to 3xc3x9710xe2x88x921 mol, per mol of silver halide contained in the same lightsensitive emulsion layer.
One or two or more couplers represented by the general formula (MC-I) can be incorporated in the lightsensitive material. The couplers can be incorporated in the same layer or in different layers. The same can be applied to the coupler represented by the general formula (MC-II). Further, the lightsensitive material can be simultaneously loaded with the coupler of the general formula (MC-I) and the coupler of the general formula (MC-II).
When the lightsensitive layer has a unit constitution including a plurality of lightsensitive emulsion layers with identical color sensitivities but with different speeds, it is preferred that the content of each coupler per mol of silver halide be in the range of 2xc3x9710xe2x88x923 to 1xc3x9710xe2x88x921 mol in a low-speed layer, 3xc3x9710xe2x88x922 to 3xc3x9710xe2x88x921 mol in an intermediate-speed layer, and 3xc3x9710xe2x88x922 to 3xc3x9710xe2x88x921 mol in a high-speed layer.
The coupler represented by the general formula (MC-1) or (MC-II) according to the present invention can be introduced in the lightsensitive material by various conventional dispersion methods. The introduction is preferably performed by an oil-in-water dispersion method of dispersing oil drops in water wherein the coupler is dissolved in a high-boiling organic solvent (in combination with a low-boiling solvent if necessary), emulsified and dispersed in an aqueous gelatin solution in the presence of a surfactant, and added to a silver halide emulsion.
Examples of the high-boiling solvent used in this oil-in-water dispersion method are described in, e.g., U.S. Pat. No. 2,322,027. Practical examples of steps, effects, and impregnating latexes of a latex dispersion method as one polymer dispersion method are described in, e.g., U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-B-53-41091, and EP029104. Dispersion using an organic solvent-soluble polymer is described in PCT International Publication W088/00723.
Examples of the high-boiling solvent usable in the abovementioned oil-in-water dispersion method are phthalic acid esters (e.g., dibutylphthalate, dioctylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-tert-amylphenyl)isophthalate, and bis(1,1-diethylpropyl)phthalate), esters of phosphoric acid and phosphonic acid (e.g., diphenylphosphate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, dioctylbutylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, and di-2-ethylhexylphenylphosphate), benzoic acid esters (e.g., 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate, and 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecaneamide and N,N-diethyllaurylamide), alcohols and phenols (e.g., isostearylalcohol, 2,4-di-tert-amylphenol, and glycerin mono-oleyl), aliphatic esters (e.g., dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanate, tributyl citrate, diethylazelate, isostearyllactate, and trioctyltosylate), aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (paraffins containing 10% to 80% of chlorine), trimesic acid esters (e.g., tributyl trimeslate), dodecylbenzene, diisopropylnaphthalene, phenols (e.g., 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, and 4-(4-dodecyloxyphenylsulfonyl)phenol), carboxylic acids (e.g., 2-(2,4-di-tert-amylphenoxy) butyric acid and 2-ethoxyoctanedecanic acid), alkylphosphoric acids (e.g., di-(2-ethylhexyl)phosphoric acid and diphenylphosphoric acid). In addition to the above high-boiling solvents, compounds described in, e.g., JP-A-6-258803, the disclosure of which is herein incorporated by reference, can also be preferably used as high-boiling solvents.
Of these compounds, phosphoric acid esters are preferable, and the combination of phosphoric acid esters with alcohols or phenols is also preferable.
In the present invention, the weight ratio of a high-boiling organic solvent to the coupler represented by formula (MC-1) is preferably 0 to 2.0, more preferably, 0.01 to 1.0, and most preferably, 0.01 to 0.5.
As a co-solvent, it is also possible to use an organic solvent (e.g., ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide) having a boiling point of 30xc2x0 C. to about 160xc2x0 C., in combination.
In the lightsensitive material of the present invention, it is only essential that at least one silver halide emulsion layer (preferably, green-sensitive emulsion layer) containing the coupler represented by the general formula (MC-1) or (MC II) according to the present invention be disposed on a support. The general lightsensitive material can be constituted by coating a support with at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer in this sequence. The coating may be performed in a sequence different therefrom.
In the present invention, it is preferred that the coating be performed in the sequence of, from the side close to the support, the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer. Further, it is preferred that each of the color sensitive layers have a unit constitution including a plurality of lightsensitive emulsion layers with different speeds. It is especially preferred that each of the color sensitive layers have a three-layer unit constitution composed of three lightsensitive emulsion layers consisting of a low-speed layer, an intermediate-speed layer and a high-speed layer arranged in this sequence from the side close to the support. Although the coupler represented by the general formula (MC-1) or (MC-II) according to the present invention can be incorporated in any of a low-speed layer, an intermediate-speed layer and a high-speed layer, it is preferred that the incorporation be effected in a low-speed layer.
In the lightsensitive material of the present invention, a spectral sensitization is effected in blue, green and red sensitivities. The wavelength realizing the maximum value of sensitivity of each lightsensitive layer is preferably in the range of 430 to 460 nm with respect to a blue-sensitive layer, 520 to 560 nm with respect to a green-sensitive layer, and 600 to 650 nm with respect to a red-sensitive layer.
The lightsensitive material of the present invention may include a lightsensitive emulsion layer exhibiting a sensitivity in wavelength regions other than the above blue, green and red sensitivities according to necessity. In particular, faithfulness in color reproduction can be enhanced by disposing such a fourth lightsensitive layer that the wavelength realizing the maximum value of sensitivity is in the range of 480 to 530 nm and by restricting the development of a red-sensitive layer as a function of development of the layer. This is preferably applied to the lightsensitive material of the present invention.
In the present invention, in addition to the coupler capable of forming a dye which is in a complementary color relationship with the color sensitivity of emulsion, a coupler which forms a color in other hue may be mixed and used. For example, in the high-speed layer and intermediate-speed layer of a green-sensitive emulsion unit, not only the coupler of the general formula (MC-I) according to the present invention but also a cyan coloring coupler or black coloring coupler can be mixed to thereby enhance a shadow descriptive capability.
Moreover, the coupler of the general formula (MC-I) or (MC-II) according to the present invention may be used in combination with other magenta couplers. Other magenta couplers for combination use are preferably 1-phenyl-3-acylamino-5-pyrazolone magenta couplers, more preferably couplers represented by the following formulae (MCP-1), (MCP-2) and (MCP-3). 
When the coupler of the general formula (MC-I) or (MC-II) according to the present invention is used in combination with other magenta couplers, the former is preferably used in a molar ratio, relative to the latter, of 30% or more, more preferably 50% or more.
When the coupler of the general formula (MC-I) or (MC-II) according to the present invention is used in combination with other magenta couplers, the total content of the couplers is in the range of 0.01 to 10 g, preferably 0.1 to 2 g, per m2 of lightsensitive material. The coupler content is suitably in the range of 1xc3x9710xe2x88x923 to 1 mol, preferably 2xc3x9710xe2x88x923 to 3xc3x9710xe2x88x921 mol, per mol of silver halide contained in the same lightsensitive emulsion layer.
The lightsensitive material of the present invention may further be loaded with a competing compound (compound which reacts with color developing agent in an oxidized form while competing with image forming couplers but does not form any dye images). The competing compound can be, for example, a reducing compound selected from among hydroquinones, catechols, hydrazines, sulfonamidophenols, etc. or a compound which couples with color developing agent in an oxidized form but substantially does not form color images (e.g., any of non-dye-forming couplers as disclosed in DE No. 1,155,675, GB No. 861,138 and U.S. Pat. Nos. 3,876,428 and 3,912,513 or any of flow-out couplers as disclosed in JP-A-6-83002).
The competing compound is preferably added to a lightsensitive emulsion layer containing the magenta coupler of the general formula (MC-I) or (MC-II) according to the present invention or a non-lightsensitive layer. More preferably, the addition is effected to lightsensitive emulsion layers containing the magenta coupler of the general formula (MC-I) or (MC-II) according to the present invention. The addition amount of competing compound is in the range of 0.01 to 10 g, preferably 0.05 to 5.0 g, per m2 of lightsensitive material. The addition amount is in the range of 1 to 1000 mol %, preferably 20 to 500 mol %, based on the coupler of the general formula (MC-I) or (MC-II) according to the present invention.
In the lightsensitive material of the present invention, a non-color-forming interlayer may be incorporated in a lightsensitive unit of the same color sensitivity. Further, a compound which can be selected as the above competing compound is preferably contained in the interlayer.
For preventing the deterioration of photographic performance by formaldehyde gas, it is preferred that the lightsensitive material of the present invention be loaded with a compound capable of reacting with formaldehyde gas to thereby immobilize it as described in U.S. Pat. Nos. 4,411,987 and 4,435,503.
Various techniques and organic and inorganic materials which can be used in the silver halide photographic lightsensitive materials of the invention and silver halide photographic emulsions used therein are generally those described in Research Disclosure No. 308119 (1989), ditto 37038 (1995), ditto 40145 (1997), the disclosures of which are incorporated herein by reference.
In addition, more specifically, techniques and inorganic and organic materials usable in color photographic materials of the present invention and in silver halide emulsion used therein are described in portions of EP436,938A2 and patents cited below.
The lightsensitive material of the present invention can be developed by a conventional development processing. The pH value of a color developer for use in the processing is to be 9.5 or higher. However, the exertion of the effect of the present invention is striking in the processing with the use of a color developer having a pH value of 11.0 or higher. The exertion of the effect of the present invention is the most striking in the processing with the use of a color developer having a pH value of 11.5 or higher.
The development processing preferably employed in the present invention will be described below.
Known developing agents can be used in the first black and white developer and replenisher thereof for use in the present invention. As developing agents, there can be mentioned, for example, dihydroxybenzenes (e.g., hydroquinone and hydroquinonemonosulfonates), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols, ascorbic acid and heterocyclic compounds such as a condensate of 1,2,3,4-tetrahydroquinoline ring and indoline ring described in U.S. Pat. No. 4,067,872. These can be used individually or in combination. Preferred developing agents are potassium hydroquinonemonosulfonate and sodium hydroquinonemonosulfonate.
The preservative for use in the first black and white developer and replenisher according to the present invention preferably consists of, for example, a sulfite or a bisulfite. The sulfite concentration of the developer is in the range of 0.01 to 10 mol/liter (liter hereinafter also referred to as xe2x80x9cLxe2x80x9d), preferably 0.1 to 1 mol/L. Also, hydroxylamines of the general formula (I) of JP-A-3-144446 can be used as the preservative.
Furthermore, in the first black and white developer and replenisher according to the present invention, use can be made of, for example, a buffer (e.g., a carbonate, a borate, an alkanolamine or sulfosalicylic acid), a hydroxide (e.g., potassium hydroxide or sodium hydroxide), a dissolution auxiliary (e.g., a polyethylene glycols), a sensitizer (e.g., a quaternary ammonium salt), a silver halide solvent (e.g., KSCN or NaSCN), a development accelerator, a surfactant and a film hardener.
The pH value of the first black and white developer and replenisher according to the present invention is preferably in the range of 8.0 to 11.0, more preferably 9.0 to 10.5, and most preferably 9.5 to 10.0.
The standard processing time with the use of the first black and white developer according to the present invention is 6 min. Sensitization and desensitization cab be effected by appropriately changing the processing time. The processing time is generally changed within the range of 3 to 18 min.
The quantity of replenisher fed to the first black and white developer according to the present invention is generally in the range of 2 to 2.5 L per m2 of processed lightsensitive material. In recent years, for reducing the amount of waste liquid, 0.5 to 1.5 L processing is also being carried out.
It is preferred to minimize the contact area between liquid and air in the processing solution tank and the replenisher tank from the viewpoint that an oxidation deterioration can be prevented. The contact area of photographic processing solution with air in the processing solution tank and the replenisher tank can be expressed by the open ratio defined as:
open ratio=[area of contact of processing solution with air (cm2)]/[volume of processing solution (cm3)].
This open ratio is preferably 0.1 or less, more preferably in the range of 0.001 to 0.05. The lowering of the open ratio can be accomplished not only by disposing a shield such as a floating cover on the surface of photographic processing solution of the processing tank and replenisher tank but also by the method of JP-A-1-82033 in which a movable cover is used or the method of JP-A-63-216050 in which a slit development processing method is conducted. The lowering of the open ratio is preferably applied to not only the two steps of color development and black and white development but also all the subsequent steps such as bleaching, bleach-fix, fixing, washing and stabilization. Further, the quantity of replenisher can be reduced by employing means for suppressing the accumulation of bromide ions in the developer.
The reversal bath or light fogging step conventionally employed after the first black and white development can be omitted in the present invention. However, when it is not omitted, known fogging agents, for example, stannous ion complex salts such as stannous ion/organophosphate complex salts (U.S. Pat. No. 3,617,282), stannous ion organophosphonocarboxylate complex salts (JP-B-56-32616) and stannous ion/aminopolycarboxylate complex salts (U.S. Pat. No. 1,209,050) and boron compounds such as boron hydride compounds (U.S. Pat. No. 2,984,567) and heterocyclic amineboran compounds (GB No. 1,011,000) are used in the reversal bath. The pH value of the reversal bath widely ranges from the acid region to the alkali region, depending on the type of fogging agent. The pH value is in the range of 2 to 12, frequently 2.5 to 10, and especially 3 to 9.
In the present invention, the color developer contains an aromatic primary amine color developing agent. The color developing agent is used in an amount of 1 to 20 g, preferably 2 to 15 g, per L of color developer.
Color developing agents may be used individually or in combination. Specific compounds will be listed below, to which, however, the color developing agents of the present invention are in no way limited.
D-1: N,N-diethyl-p-phenylenediamine,
D-2: 2-amino-5-diethylaminotoluene,
D-3: 2-amino-5-(N-ethyl-N-laurylamino)toluene,
D-4: 4-[N-ethyl-N-(xcex2-hydroxyethyl)amino]aniline,
D-5: 2-methyl-4-[N-ethyl-N-(xcex2-hydroxyethyl)amino]aniline,
D-6: 4-amino-3-methyl-N-ethyl-N-[xcex2-(methanesulfonamido)ethyl]-aniline,
D-7: N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide,
D-8: N,N-dimethyl-p-phenylenediamine,
D-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline,
D-10: 4-amino-3-methyl-N-ethyl-N-xcex2-ethoxyethylaniline, and
D-11: 4-amino-3-methyl-N-ethyl-N-xcex2-butoxyethylaniline.
These color developing agents are generally used in the form of a salt, such as a hydrochloride, a sulfate, a phosphate or a p-toluenesulfonate, or in the form of a hydrate of salt.
The color developing agents preferably employed in the present invention are D-4, D-5 and D-6.
In the present invention, if necessary, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite or potassium metasulfite, or a carbonyl compound sulfite adduct, can be added as a preservative to the color developer. The addition amount thereof is preferably 20 g or less, more preferably 10 g or less, and most preferably 0.05 to 5 g, per L of color developer.
In the present invention, a colorless compound forming competing coupler may be added to the color developer in order to regulate the gradation of color image. Colorless compound forming competing couplers are described in U.S. Pat. Nos. 2,742,832, 3,520,690 and 3,645,737 and JP-B""s 44-9504, 44-9506 and 44-9507. As especially preferably employed compounds, there can be mentioned, for example, citrazinic acid, J-acid, H-acid and resorcinol. Among these, citrazinic acid is most preferred. In the addition of colorless compound forming competing couplers to the color developer, the addition amount is in the range of 1 to 10 mmol/L.
In the present invention, it is not preferable to use hydroxylamine as a preservative. The reason is that its compatibility with the color developer is poor because of the exhibition of a noncoloring development activity, so that desirable photographic properties (gradation) cannot be obtained. As other preservatives for color developers, there can be mentioned sulfinic acids, xcex1-hydroxyketones and xcex1-aminoketones described in JP-A-63-44656, various saccharides described in JP-A-63-36244, monoamines described in, for example, JP-A""s 63-4235, 63-24254, 63-21647, 63-146040, 63-27841 and 63-25654, diamines described in, for example, JP-A""s 63-30845, 63-146040 and 63-43439, polyamines described in JP-A""s 63-21647 and 63-26655, polyamines described in JP-A-63-44655, alcohols described in JP-A""s 63-43140 and 63-53549, oximes described in JP-A-63-56654 and tertiary amines described in JP-A-63-239447.
As other preservatives, for example, various metals described in JP-A""s 57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349 and aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 may be contained therein if necessary.
The color developer for use in the present invention can contain other compounds known as components for developer.
Appropriate alkali agent and pH buffer are added to the color developer for use in the present invention in order to maintain the pH value within the above range. As the alkali agent and pH buffer, there can be employed carbonates such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate; alkali hydroxides such as sodium hydroxide and potassium hydroxide; phosphates such as trisodium phosphate and dipotassium phosphate; borates such as potassium borate and sodium tetraborate; and organic acid salts such as dipotassium 5-sulfosalicylate and disodium 4-sulfosalicylate.
The above alkali agent and pH buffer are added to the color developer in an amount of 0.01 to 0.5 mol/L, preferably 0.01 to 0.2 mol/L.
Furthermore, in the color developer, various chelating agents can be used as a precipitation-preventing agent for calcium and magnesium or in order to increase the stability of color developer. Chelating agents preferably consist of organic acid compounds, examples of which include aminopolycarboxylic acids, organophosphonic acids and phosphonocarboxylic acids. Specific examples of such chelating agents include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenesulfonic acid, ethylenediamine-N,N,Nxe2x80x2,Nxe2x80x2-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 1-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,Nxe2x80x2-bis(2-hydroxybenzyl)ethylenediamine-N,Nxe2x80x2-diacetic acid and 1,2-dihydroxyoxybenzene-3,5-disulfonic acid. These chelating agents may be used in combination if necessary.
The addition amount of chelating agents is preferably in the range of 0.01 to 20 g, more preferably 0.1 to 10 g, per L of color developer. If necessary, an arbitrary development accelerator can be added to the color developer. For attaining the maximum exhibition of development activity, a thioether-type fog accelerator may be added to the color developer. As thioether fogging agents, use is made of thioether compounds described in, for example, JP-B""s 37-16088, 37-5987, 38-7826, 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247. Further, use can be made of amine compounds such as ethylenediamine. Among these compounds, 3,6-dithiaoctane-1,8-diol is preferred. When the fogging agent is added to the color developer, the addition amount thereof is in the range of about 1 to 20 mmol/L.
With respect to the quantity of replenisher for the color developer of the present invention, 40 to 4000 milliliters/m2 are satisfactory in continuing the processing. The amount of waste liquid can be minimized by minimizing the quantity of replenisher. Therefore, it is preferred to minimize the quantity of replenisher, as long as the developer is stable. (Hereinafter, milliliters will be referred to as xe2x80x9cmLxe2x80x9d.) The quantity of replenisher is preferably less than 2000 mL/m2, more preferably less than 1600 mL/m2.
In the present invention, the color development is followed by a desilvering conducted with the use of a processing solution having bleaching capacity. In the desilvering, use is made of a bleaching solution, a bleach-fix solution or both. Such a processing solution contains a bleaching agent. As the bleaching agent, there can be employed, for example, compounds of polyvalent metals such as iron (III), peracids, quinones and nitro compounds. Examples of representative preferably employed bleaching agents include bleaching agents of organic complex salts of iron (III), for example, iron complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol ether diaminetetraacetic acid and 1,3-propylenediaminetetraacetic acid described in JP-A-4-121739, right lower column of page 4 to left upper column of page 5; carbamoyl bleaching agents described in JP-A-4-73647; heterocyclic bleaching agents described in JP-A-4-174432; ferric complex salt of N-(2-carboxyphenyl)iminodiacetic acid and related bleaching agents described in EP No. 520457; ferric complex salt of ethylenediamine-N-2-carboxyphenyl-N,Nxe2x80x2,Nxe2x80x2-triacetic acid and related bleaching agents described in EP No. 530828A1; bleaching agents described in EP No. 501479; bleaching agents described in JP-A-4-127145; and ferric salt of aminopolycarboxylic acid and related salts described in JP-A-5-303186 and JP-A-3-144446 (page 11).
Organic aminocarboxylic acid iron (III) complex salts are especially useful in both the bleaching solution and the bleach-fix solution. Although the pH value of the bleaching solution and bleach-fix solution containing the above organic aminocarboxylic acid iron (III) complex salts generally ranges from 4.0 to 8.0, the processing can be conducted at lower pH values in order to expedite the processing.
In the present invention, in addition to the bleaching agent, a re-halogenating agent as described in page 12 of JP-A-3-144446 mentioned above, a pH buffer, known additives, an aminopolycarboxylic acid, an organophosphonic acid, etc. can be used in the processing bath having bleaching capacity.
Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or prebath thereof (conditioner). As these bleaching accelerators, there can be employed, for example, mercapto group- or disulfido group-having compounds described in U.S. Pat. No. 3,893,858, DE U.S. Pat. No. 1,290,821, GB No. 1,138,842, JP-A-53-95630 and Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in U.S. Pat. No. 3,706,561; iodides described in JP-A-58-16235; polyoxyethylene oxides described in DE U.S. Pat. No. 2,748,430; and polyamine compounds described in JP-B-45-8836. Still further, compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be incorporated in the lightsensitive material. These bleaching accelerators are especially effective in the bleach-fix of photographic color lightsensitive materials. Mercapto compounds described in GB No. 1,138,842 and JP-A-2-190856 are most preferred.
For preventing bleach stains, it is preferred that, in addition to the above compounds, an organic acid be added to the processing solution having bleaching capacity (bleaching solution or bleach-fix solution). Especially preferred organic acids are compounds whose acid dissociation constant (pKa) ranges from 2 to 5. Preferred examples of such compounds include acetic acid, lactic acid, malonic acid, maleic acid, glutaric acid, succinic acid, propionic acid and hydroxyacetic acid.
It is preferred that these organic acids be contained in an amount of 0.005 to 3 mol per L of processing solution having bleaching capacity. Although it is preferred that the bleaching be performed immediately after the color development, in the reversal processing, a conditioner (may be a bleaching accelerator solution) is generally used therebetween.
The conditioner can contain chelating agents of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid and cyclohexanediaminetetraacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and various bleaching accelerators such as thioglycerol, aminoethanethiol and sulfoethanethiol. Further, for the purpose of scum prevention, it is preferred to add, to the conditioner, sorbitan esters of fatty acids substituted with ethylene oxide, described in U.S. Pat. No. 4,839,262; and polyoxyethylene compounds described in U.S. Pat. No. 4,059,446 and Research Disclosure, vol. 191, 19104 (1980). These compounds, although can be used in an amount of 0.1 to 20 g per L of conditioner, are preferably added in an amount of 1 to 5 g per L of conditioner.
Further, the conditioner can contain an image stabilizing agent as described later. The pH value of the conditioner is generally in the range of 3 to 11, preferably 4 to 9, and more preferably 4.5 to 7. The time of processing with the use of the conditioner is preferably in the range of 20 sec to 15 min, more preferably 20 sec to 100 sec, and most preferably 20 sec to 60 sec. The quantity of replenisher for the conditioner is preferably in the range of 30 to 3000 mL, more preferably 50 to 1500 mL, per m2 of lightsensitive material. The temperature of processing with the use of the conditioner is preferably in the range of 20 to 50xc2x0 C., more preferably 30 to 40xc2x0 C.
In the present invention, the desilvering may be followed by washing and processing with the use of a stabilizer bath in this sequence. Alternatively, the desilvering may be followed by processing with the use of a stabilizer directly without performing washing. The amount of water used in the washing step can be set within a wide range, depending on the properties of lightsensitive material (for example, attributed to the employed material of coupler, etc.), use, temperature of washing water, number of washing tanks (number of stages), replenishing method such as counter current or fair current and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multistage counter current system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers, vol. 64, pp. 248 to 253 (May, 1955). Although the amount of washing water can be extremely reduced, the multistage counter current system described in this literature encounters a problem such that the residence time of water in the tank is increased to thereby invite growth of bacteria with the result that resultant suspended matter sticks to the lightsensitive material. In the processing of the present invention, the method of JP-A-62-288838 in which the amount of calcium ions and magnesium ions is decreased can very effectively utilized as a countermeasure to the above problem. Also, there can preferably be employed isothiazolone compounds and cyabenzazoles as described in JP-A-57-8542; chlorinated bactericides such as sodium chloroisocyanurate; other benzotriazoles; and bactericides described in xe2x80x9cBokin Bokabizai No Kagaku (Chemistry of Antibacterial Mildewproofing Agents)xe2x80x9d written by Hiroshi Horiguchi and published by Sankyo Shuppan (1986), xe2x80x9cBiseibutsu No Mekkin, Sakkin, Bokabigijutsu (Microorganism Sterilization, Pasteurization and Mildewproofing Technology)xe2x80x9d edited by the Hygienic Technology Association and published by Kogyo Gijutsu Kai (Industrial Technology Association) (1982) and xe2x80x9cBokin Bokabizai Jiten (Antibacterial Mildewproofing Agent Cyclopedia)xe2x80x9d edited by the Antibacterial Mildewproofing Society of Japan (1986).
As the stabilizer of the present invention, although stabilizers containing formaldehyde are generally employed, there can also be used other known stabilizers and processing methods as described in, for example, U.S. Pat. Nos. 4,786,583 and 4,859,574 and JP-A""s 3-33847, 4-270344, 4-313753, 4-359249, 5-34889, 5-165178, 57-8543, 58-14834 and 60-220345.
A compound capable of stabilizing a dye image (hereinafter referred to as xe2x80x9cimage stabilizing agentxe2x80x9d) is contained in the stabilizer or conditioner of the present invention. The image stabilizing agent can be, for example, any of formaldehyde, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adducts, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, dimethylolurea, and N-methylol compounds such as N-methylolpyrazole. In the present invention, it is preferred that the free formaldehyde concentration of the solution be in the range of 0 to 0.01%, especially 0 to 0.005%, from the viewpoint that the effect of the invention can be enhanced. As the image stabilizing agent for attaining the above free formaldehyde concentration, there can be preferably employed m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolazoles of JP-A-4-270344 such as N-methylolpyrazole, and azolylmethylamines of JP-A-4-313753 such as N,Nxe2x80x2-bis(1,2,4-triazol-1-ylmethyl)piperazine.
The content of the above image stabilizing agent is preferably in the range of 0.001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per L of stabilizer. For preventing the occurrence of water spots at the drying of processed lightsensitive material, it is preferred that the stabilizer of the present invention contain various surfactants. Examples of such surfactants include polyethylene glycol nonionic surfactants, polyhydric alcohol nonionic surfactants, alkylbenzenesulfonate anionic surfactants, higher alcohol sulfate anionic surfactants, alkylnaphthalenesulfonate anionic surfactants, quaternary ammonium salt cationic surfactants, amine salt cationic surfactants, amino salt amphoteric surfactants and betaine amphoteric surfactants. The use of nonionic surfactants is preferred. Nonionic surfactants such as alkylpolyethylene oxides, alkylphenoxypolyethylene oxides and alkylphenoxypolyhydroxypropylene oxides are especially preferred.
It is preferred that a chelating agent as heavy metal scavenger be added to the stabilizer of the present invention, from the viewpoint that the stability of the stabilizer is enhanced and that any contamination can be reduced. As the chelating agent, there can be employed the same compounds as added to the above developer and bleaching solution. Further, an antibacterial/mildewproofing agent is preferably added to the stabilizer of the present invention in order to prevent the occurrence of bacteria and mildew. Commercially available antibacterial/mildewproofing agents can be used.
The pH value of each of the stabilizer and washing water according to the present invention is in the range of 4 to 9, preferably 5 to 8. The processing temperature and processing time, although can be set in variation depending on, for example, the properties and usage of lightsensitive material, are generally in the range of 15 to 45xc2x0 C. and 20 sec to 10 min, preferably 25 to 40xc2x0 C. and 30 sec to 2 min, respectively. The anti-contamination effect of the stabilizer of the present invention is striking when the desilvering is directly followed by processing with the use of the stabilizer without performing washing.
The quantity of replenisher for the stabilizer of the present invention is preferably in the range of 200 to 2000 mL per m2 of lightsensitive material. The overflow solution resulting from the above washing and/or stabilizer replenishing can be recycled to desilvering and other steps.
Ion exchange or ultrafiltration may be effected for reducing the amount of washing water consumed. Ultrafiltration is preferred. The processing solutions of the present invention are applied at 10 to 50xc2x0 C. Although generally the temperature of 33 to 38xc2x0 C. is standard, the temperature can be raised so as to expedite the processing and reduce the processing time. Contrarily, the temperature can be lowered so as to accomplish the improvement of image quality and the improvement of processing solution stability.